CN106823852B - A kind of preparation method of phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane - Google Patents
A kind of preparation method of phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane Download PDFInfo
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- CN106823852B CN106823852B CN201710211960.6A CN201710211960A CN106823852B CN 106823852 B CN106823852 B CN 106823852B CN 201710211960 A CN201710211960 A CN 201710211960A CN 106823852 B CN106823852 B CN 106823852B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
- B01D71/14—Esters of organic acids
- B01D71/16—Cellulose acetate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/36—Introduction of specific chemical groups
Abstract
A kind of preparation method of phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane, it is related to a kind of preparation method of infiltrating and vaporizing membrane.The invention aims to solve the problem of the high low separation efficiency of existing pervaporation membrane separating method energy consumption and pollute the environment.Method: one, phenolic resin charcoal is prepared；Two, the phenolic resin charcoal powder that partial size is 50nm~60nm is prepared；Three, the dry phenolic resin charcoal powder of preparation；Four, preparation treated phenolic resin charcoal powder；Five, uniform mixed liquor I is prepared；Six, mixed liquor II is prepared；Seven, mixed solution III is prepared；Eight, it is poured, knifing, obtains phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane.The present invention can get a kind of preparation method of phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane.
Description
Technical field
The present invention relates to a kind of preparation methods of infiltrating and vaporizing membrane.
Background technique
With the continuous development of human civilization, non-renewable fossil fuel such as natural gas, coal, petroleum etc. is slowly exhausted, people
Class is constantly looking for always the new energy and is replacing the energy to solve energy crisis.World petroleum price rises steadily, and environment is dirty
Dye problem grows in intensity, and global warming issue increasingly sharpens, and it is extremely urgent to develop new clean energy resource.With reproducible life
Substance is raw material, can reduce the influence of energy crisis with the ethyl alcohol of fermentation method preparation high-purity, reduce atmosphere pollution and reduction
Greenhouse effects and receive significant attention.Fermentation method prepares ethyl alcohol and is primarily present two problems: one, in feed liquid ethyl alcohol separation；Two,
When concentration of alcohol is more than 8% in fermentation liquid, inhibition can be generated to Yeast Growth, or even kill saccharomycete.It is used at present
The method of separating alcohol mainly have solvent extraction hair, carbon dioxide air lift and way of distillation etc., these separation methods exist a large amount of
Energy consumption and pollution.Separation method more than comparing, low energy consumption for pervaporation membrane separating method, not can cause environmental pollution；Together
When during the separation process, the saccharomycete in fermentation liquid will not be killed；With the continuous progress of separation process, ethyl alcohol is constantly divided
It separates out and, so that concentration of alcohol in feed liquid is not exceeded 8%, be carried out continuously fermentation process, realize continuous production.
Summary of the invention
It is high the invention aims to solve existing pervaporation membrane separating method energy consumption, low separation efficiency and environment is made
The problem of at pollution, and a kind of preparation method of phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane is provided.
A kind of preparation method of phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane, specifically by following
What step was completed:
One, it prepares phenolic resin charcoal: bark is clayed into power, then dry 12h at being 100 DEG C~105 DEG C in temperature
~30h obtains dry bark fines；Dry bark fines are mixed with phenolic resin again, then low whipping speed is 180r/
Magnetic agitation 4h~6h under min~200r/min obtains the mixture of dry bark fines and phenolic resin；By dry tree
The mixture of skin powder and phenolic resin solidifies 1h~3h in the case where pressure is 8MPa~12MPa and temperature is 160 DEG C~200 DEG C,
High-temperature process 1h~1.5h at being again 300 DEG C~900 DEG C in nitrogen atmosphere and temperature, obtains phenolic resin charcoal；
The bark fines of drying described in step 1 and the mass ratio of phenolic resin are 1:(0.5~2)；
Two, phenolic resin charcoal is ground, then dries 12h~30h at being 100 DEG C~140 DEG C in temperature, obtained
Partial size is the phenolic resin charcoal powder of 50nm~60nm；
Three, the phenolic resin charcoal powder that partial size is 50nm~60nm is wrapped up using filter paper, then is placed in rope
It in family name's extractor, then uses toluene for solvent, extracts 20h~30h, the biological powdered carbon after being extracted under nitrogen protection；It will
Biological powdered carbon after extracting is dried at normal temperature, obtains dry phenolic resin charcoal powder；
Four, by dry phenolic resin charcoal powder, mass fraction be 37% methanol solution and mass fraction be
20% sodium hydroxide solution mixing, then the magnetic in the case where temperature is 40 DEG C~60 DEG C and mixing speed is 180r/min~200r/min
Power stirs 4h~6h, then cooled to room temperature reuses distilled water and cleans 3 times~5 times, be finally putting into temperature be 100 DEG C~
In 140 DEG C of vacuum oven it is dry for 24 hours~48h, the phenolic resin charcoal powder that obtains that treated；
The quality of the phenolic resin charcoal powder of drying described in step 4 and the methanol that mass fraction is 37% are molten
The volume ratio of liquid is (10g~15g): 100mL；
The hydroxide that the quality and mass fraction of the phenolic resin charcoal powder of drying described in step 4 are 20%
The volume ratio of sodium solution is (10g~15g): 10mL；
Five, by treated, phenolic resin charcoal powder, vinyltriethoxysilane and n-hexane are mixed, and are mixed
Liquid I is closed, ultrasonic oscillation device is reused and 20min~40min is handled to I ultrasonic vibration of mixed liquor, then low whipping speed is 180r/
Magnetic agitation 40min~60min under min~200r/min obtains uniform mixed liquor I；
The mass ratio of vinyltriethoxysilane described in step 5 and treated phenolic resin charcoal powder
For (0.5~2): 1；
The quality of phenolic resin charcoal powder that treated described in step 5 and the volume ratio of n-hexane are
(0.01g~0.05g): 70mL；
Six, dimethyl silicone polymer and n-hexane are mixed, then low whipping speed is magnetic under 180r/min~200r/min
Power stirs 0.5h~2.5h, obtains mixed liquor II；
The quality of dimethyl silicone polymer described in step 6 and the volume ratio of n-hexane are (0.8g~1g): 70mL；
Seven, uniform mixed liquor I and mixed liquor II are mixed, then low whipping speed is magnetic under 180r/min~200r/min
Power stirs 60min~120min, adds ethyl orthosilicate, then low whipping speed is that magnetic force stirs under 180r/min~200r/min
30min~60min is mixed, dibutyl tin dilaurate is added, then low whipping speed is magnetic force under 180r/min~200r/min
8min~16min is stirred, mixed solution III is obtained；
The volume ratio of ethyl orthosilicate described in step 7 and mixed liquor II is 1:(1000~1500)；
Dibutyl tin dilaurate described in step 7 and the volume ratio of mixed liquor II are 1:(5000~10000)；
Eight, cellulose acetate microfiltration membranes are impregnated into 1h~3h in deionized water, it is micro- wipes out cellulose acetate after taking-up
The deionized water of filter membrane surface, then by mixed solution III under conditions of temperature is 20 DEG C~25 DEG C and humidity is 50%~60%
It casts in the cellulose acetate microfiltration membranes of removal surface deionized water, it is micro- in cellulose acetate using knifing machine in casting process
Knifing is carried out on filter membrane, then again by the cellulose acetate microfiltration membranes for being cast with mixed solution III place at room temperature 20h~
28h, then dry 6h~8h in the baking oven that temperature is 80 DEG C obtain the enhancing ethanol selectivity infiltration of phenol-formaldehyde resin modified charcoal
Vaporize film；
The mass ratio of mixed solution III described in step 8 and cellulose acetate micro-nano filter membrane is (102~105): 10.
Advantages of the present invention:
One, phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane prepared by the present invention can be to quality point
Number is separated for 5%~20% ethanol water, and separated product is gaseous state, need to be by condensation collection processing, gained
Solution is isolated ethanol solution；
Two, the partial size of phenolic resin charcoal powder employed in the present invention is 50nm~60nm, polydimethylsiloxanes
The ordered arrangement of alkane strand is enable to separate effective free body that one polymer penetrates ethanol molecule by highly effective change
Product increases, so that phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltration evaporation membrane separation efficiency ratio be made to be not added with phenolic aldehyde
The composite membrane of resin charcoal significantly improves；In fact, the adding proportion of phenolic resin charcoal and the separation of ethanol of composite membrane
Closely related between ability, the additive amount of phenolic resin charcoal is excessive, and direct consequence is exactly dimethyl silicone polymer molecule
The ordered arrangement of chain is broken completely, and external presentation is that the mechanical performance of composite membrane is decreased obviously, and can not even be permeated
Evaporation；
Three, phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane prepared by the present invention is used for 40 DEG C
The ethanol solution of 10% concentration, separation factor 11.4, permeation flux 224.37gm-2·h-1。
The present invention can get a kind of preparation method of phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane.
Detailed description of the invention
Fig. 1 is infrared spectrogram, and 1 is treated the phenolic resin charcoal obtained in step 4 of embodiment one in Fig. 1
The infrared curve of powder, 2 be the infrared of the powder that obtains after I solvent flashing of uniform mixed liquor obtained in one step 5 of embodiment
Curve；
Fig. 2 is that the additive amount of treated phenolic resin biology powdered carbon enhances ethyl alcohol selection to phenol-formaldehyde resin modified charcoal
Property infiltrating and vaporizing membrane surface and water contact angle influence diagram, 1 is raw for the phenol-formaldehyde resin modified for preparing in embodiment one in Fig. 2
Object charcoal enhances the surface of ethanol selectivity infiltrating and vaporizing membrane and the contact angle curve of water, the 2 modification phenol to prepare in embodiment two
Urea formaldehyde charcoal enhances the surface of ethanol selectivity infiltrating and vaporizing membrane and the contact angle curve of water, and 3 be to prepare in embodiment three
Phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane surface and water contact angle curve；
Fig. 3 is that the additive amount of treated phenolic resin biology powdered carbon enhances ethyl alcohol selection to phenol-formaldehyde resin modified charcoal
Property infiltrating and vaporizing membrane surface and dehydrated alcohol contact angle influence diagram, 1 modified phenolic to be prepared in embodiment one in Fig. 3
Resin charcoal enhances the surface of ethanol selectivity infiltrating and vaporizing membrane and the contact angle curve of dehydrated alcohol, and 2 is in embodiments two
The surface of the phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane of preparation and the contact angle curve of dehydrated alcohol,
3 be surface and the dehydrated alcohol that the phenol-formaldehyde resin modified charcoal prepared in embodiment three enhances ethanol selectivity infiltrating and vaporizing membrane
Contact angle curve；
Fig. 4 is vinyltriethoxysilane with the ratio of treated phenolic resin biology powdered carbon to composite membrane separation property
Can influence, A is that phenol-formaldehyde resin modified charcoal obtained in embodiment five enhances ethanol selectivity infiltrating and vaporizing membrane in Fig. 4
The histogram of total permeation flux, B are that phenol-formaldehyde resin modified charcoal obtained in embodiment five enhances ethanol selectivity infiltration vapour
Change the histogram of the ethanol infiltration flux of film, C is that phenol-formaldehyde resin modified charcoal obtained in embodiment five enhances ethyl alcohol selection
Property infiltrating and vaporizing membrane water penetration flux histogram, D be embodiment six obtained in phenol-formaldehyde resin modified charcoal enhance second
Alcohol selectively penetrating vaporizes the histogram of total permeation flux of film, and E is phenol-formaldehyde resin modified charcoal obtained in embodiment six
Enhance the histogram of the ethanol infiltration flux of ethanol selectivity infiltrating and vaporizing membrane, F is modified phenolic resin obtained in embodiment six
Rouge charcoal enhances the histogram of the water penetration flux of ethanol selectivity infiltrating and vaporizing membrane, and G is the modification phenol that embodiment seven obtains
Urea formaldehyde charcoal enhances total permeation flux histogram of ethanol selectivity infiltrating and vaporizing membrane, and H is to change obtained in embodiment seven
Property phenolic resin charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane ethanol infiltration flux histogram, I be embodiment seven in
The histogram of the water penetration flux of obtained phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane；
Fig. 5 is vinyltriethoxysilane with the ratio of treated phenolic resin biology powdered carbon to phenol-formaldehyde resin modified
Charcoal enhances the influence diagram of ethanol selectivity infiltrating and vaporizing membrane separation, 1 modified phenolic prepared for embodiment five in Fig. 5
Resin charcoal enhances the separation factor histogram of ethanol selectivity infiltrating and vaporizing membrane, 2 modified phenolics prepared for embodiment six
Resin charcoal enhances the separation factor histogram of ethanol selectivity infiltrating and vaporizing membrane, 3 modified phenolics prepared for embodiment seven
The separation factor histogram of resin charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane；
Fig. 6 is that the additive amount of treated phenolic resin biology powdered carbon enhances ethyl alcohol selection to phenol-formaldehyde resin modified charcoal
The influence diagram of the permeation flux of property infiltrating and vaporizing membrane；The 1 phenol-formaldehyde resin modified charcoal enhancing to be prepared in embodiment one in Fig. 6
The curve of the permeation flux of ethanol selectivity infiltrating and vaporizing membrane, the 2 phenol-formaldehyde resin modified charcoal to prepare in embodiment two increase
The curve of the permeation flux of strong ethanol selectivity infiltrating and vaporizing membrane, the 3 phenol-formaldehyde resin modified charcoal to be prepared in embodiment three
Enhance the curve of the permeation flux of ethanol selectivity infiltrating and vaporizing membrane；
Fig. 7 is that the additive amount of treated phenolic resin biology powdered carbon enhances ethyl alcohol selection to phenol-formaldehyde resin modified charcoal
The influence diagram of the separation factor of property infiltrating and vaporizing membrane；The 1 phenol-formaldehyde resin modified charcoal enhancing to be prepared in embodiment one in Fig. 7
The separation factor curve of ethanol selectivity infiltrating and vaporizing membrane, the 2 phenol-formaldehyde resin modified charcoal enhancing to be prepared in embodiment two
The separation factor curve of ethanol selectivity infiltrating and vaporizing membrane, the 3 phenol-formaldehyde resin modified charcoal enhancing to be prepared in embodiment three
The separation factor curve of ethanol selectivity infiltrating and vaporizing membrane；
Fig. 8 is the operating time to enhance ethanol selectivity infiltration evaporation to phenol-formaldehyde resin modified charcoal prepared by embodiment six
The curve that film infiltration evaporation performance influences, 1 phenol-formaldehyde resin modified charcoal increasing prepare by embodiment six for the operating time in Fig. 8
The curve that strong ethanol selectivity infiltrating and vaporizing membrane permeation flux influences, 2 modification prepared by embodiment six for the operating time in Fig. 8
Phenolic resin charcoal enhances the curve that ethanol selectivity infiltrating and vaporizing membrane separation factor influences.
Specific embodiment
Specific embodiment 1: present embodiment is a kind of phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltration vapour
Change the preparation method of film, it is characterised in that this method was specifically realized by the following steps:
One, it prepares phenolic resin charcoal: bark is clayed into power, then dry 12h at being 100 DEG C~105 DEG C in temperature
~30h obtains dry bark fines；Dry bark fines are mixed with phenolic resin again, then low whipping speed is 180r/
Magnetic agitation 4h~6h under min~200r/min obtains the mixture of dry bark fines and phenolic resin；By dry tree
The mixture of skin powder and phenolic resin solidifies 1h~3h in the case where pressure is 8MPa~12MPa and temperature is 160 DEG C~200 DEG C,
High-temperature process 1h~1.5h at being again 300 DEG C~900 DEG C in nitrogen atmosphere and temperature, obtains phenolic resin charcoal；
The bark fines of drying described in step 1 and the mass ratio of phenolic resin are 1:(0.5~2)；
Two, phenolic resin charcoal is ground, then dries 12h~30h at being 100 DEG C~140 DEG C in temperature, obtained
Partial size is the phenolic resin charcoal powder of 50nm~60nm；
Three, the phenolic resin charcoal powder that partial size is 50nm~60nm is wrapped up using filter paper, then is placed in rope
It in family name's extractor, then uses toluene for solvent, extracts 20h~30h, the biological powdered carbon after being extracted under nitrogen protection；It will
Biological powdered carbon after extracting is dried at normal temperature, obtains dry phenolic resin charcoal powder；
Four, by dry phenolic resin charcoal powder, mass fraction be 37% methanol solution and mass fraction be
20% sodium hydroxide solution mixing, then the magnetic in the case where temperature is 40 DEG C~60 DEG C and mixing speed is 180r/min~200r/min
Power stirs 4h~6h, then cooled to room temperature reuses distilled water and cleans 3 times~5 times, be finally putting into temperature be 100 DEG C~
In 140 DEG C of vacuum oven it is dry for 24 hours~48h, the phenolic resin charcoal powder that obtains that treated；
The quality of the phenolic resin charcoal powder of drying described in step 4 and the methanol that mass fraction is 37% are molten
The volume ratio of liquid is (10g~15g): 100mL；
The hydroxide that the quality and mass fraction of the phenolic resin charcoal powder of drying described in step 4 are 20%
The volume ratio of sodium solution is (10g~15g): 10mL；
Five, by treated, phenolic resin charcoal powder, vinyltriethoxysilane and n-hexane are mixed, and are mixed
Liquid I is closed, ultrasonic oscillation device is reused and 20min~40min is handled to I ultrasonic vibration of mixed liquor, then low whipping speed is 180r/
Magnetic agitation 40min~60min under min~200r/min obtains uniform mixed liquor I；
The mass ratio of vinyltriethoxysilane described in step 5 and treated phenolic resin charcoal powder
For (0.5~2): 1；
The quality of phenolic resin charcoal powder that treated described in step 5 and the volume ratio of n-hexane are
(0.01g~0.05g): 70mL；
Six, dimethyl silicone polymer and n-hexane are mixed, then low whipping speed is magnetic under 180r/min~200r/min
Power stirs 0.5h~2.5h, obtains mixed liquor II；
The quality of dimethyl silicone polymer described in step 6 and the volume ratio of n-hexane are (0.8g~1g): 70mL；
Seven, uniform mixed liquor I and mixed liquor II are mixed, then low whipping speed is magnetic under 180r/min~200r/min
Power stirs 60min~120min, adds ethyl orthosilicate, then low whipping speed is that magnetic force stirs under 180r/min~200r/min
30min~60min is mixed, dibutyl tin dilaurate is added, then low whipping speed is magnetic force under 180r/min~200r/min
8min~16min is stirred, mixed solution III is obtained；
The volume ratio of ethyl orthosilicate described in step 7 and mixed liquor II is 1:(1000~1500)；
Dibutyl tin dilaurate described in step 7 and the volume ratio of mixed liquor II are 1:(5000~10000)；
Eight, cellulose acetate microfiltration membranes are impregnated into 1h~3h in deionized water, it is micro- wipes out cellulose acetate after taking-up
The deionized water of filter membrane surface, then by mixed solution III under conditions of temperature is 20 DEG C~25 DEG C and humidity is 50%~60%
It casts in the cellulose acetate microfiltration membranes of removal surface deionized water, it is micro- in cellulose acetate using knifing machine in casting process
Knifing is carried out on filter membrane, then again by the cellulose acetate microfiltration membranes for being cast with mixed solution III place at room temperature 20h~
28h, then dry 6h~8h in the baking oven that temperature is 80 DEG C obtain the enhancing ethanol selectivity infiltration of phenol-formaldehyde resin modified charcoal
Vaporize film；
The mass ratio of mixed solution III described in step 8 and cellulose acetate micro-nano filter membrane is (102~105): 10.
Present embodiment bark described in step 1 is shore pipe bark.
The advantages of present embodiment:
One, the phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane of present embodiment preparation can confront
The ethanol water that amount score is 5%~20% is separated, and separated product is gaseous state, need to pass through condensation collection processing,
Acquired solution is isolated ethanol solution；
Two, the partial size of phenolic resin charcoal powder employed in present embodiment is 50nm~60nm, poly dimethyl
The ordered arrangement of siloxane molecule chain by highly effective change, enable to separate one polymer through ethanol molecule effectively from
Increased by volume, so that phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltration evaporation membrane separation efficiency ratio be made to be not added with
The composite membrane of phenolic resin charcoal significantly improves；In fact, the adding proportion of phenolic resin charcoal and the ethyl alcohol of composite membrane
Closely related between separating capacity, the additive amount of phenolic resin charcoal is excessive, and direct consequence is exactly dimethyl silicone polymer
The ordered arrangement of strand is broken completely, and external presentation is that the mechanical performance of composite membrane is decreased obviously, and can not even carry out
Pervaporation；
Three, the phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane of present embodiment preparation is used for 40
DEG C 10% concentration ethanol solution, separation factor 11.4, permeation flux 224.37gm-2·h-1。
Present embodiment can get a kind of preparation of phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane
Method.
Specific embodiment 2: the differences between this implementation mode and the specific implementation mode are that: bark is worn into step 1
Powder, then 12h~for 24 hours is dried at being 105 DEG C in temperature, obtain dry bark fines；Again by dry bark fines and phenol
Urea formaldehyde mixing, then low whipping speed is magnetic agitation 4h~5h under 180r/min, obtains dry bark fines and phenolic aldehyde tree
The mixture of rouge；By the mixture of dry bark fines and phenolic resin be 8MPa~10MPa in pressure and temperature is 160 DEG C
Solidify 1h~2h at~180 DEG C, then high-temperature process 1h at being 300 DEG C~600 DEG C in nitrogen atmosphere and temperature, obtains phenolic resin
Charcoal.Other steps are same as the specific embodiment one.
Specific embodiment 3: one of present embodiment and specific embodiment one or two difference are: institute in step 1
The bark fines for the drying stated and the mass ratio of phenolic resin are 1:(0.5~1).Other steps and specific embodiment one or two
It is identical.
Specific embodiment 4: one of present embodiment and specific embodiment one to three difference are: will in step 2
Phenolic resin charcoal is ground, then dry 12h at being 100 DEG C~120 DEG C in temperature~for 24 hours, obtain partial size be 50nm~
The phenolic resin charcoal powder of 60nm.Other steps are identical as specific embodiment one to three.
Specific embodiment 5: one of present embodiment and specific embodiment one to four difference are: making in step 3
It is wrapped up, then is placed in Soxhlet extractor with the phenolic resin charcoal powder that filter paper is 50nm~60nm to partial size, then
It uses toluene for solvent, extracts 20h~for 24 hours, the biological powdered carbon after being extracted under nitrogen protection；By the charcoal after extracting
Powder is dried at normal temperature, obtains dry phenolic resin charcoal powder.Other steps and specific embodiment one to four
It is identical.
Specific embodiment 6: one of present embodiment and specific embodiment one to five difference are: will in step 4
The methanol solution that dry phenolic resin charcoal powder, mass fraction are 37% and the sodium hydroxide that mass fraction is 20% are molten
Liquid mixing, then magnetic agitation 4h~5h in the case where temperature is 40 DEG C~50 DEG C and mixing speed is 180r/min~200r/min, then
Cooled to room temperature reuses distilled water and cleans 3 times~4 times, is finally putting into the vacuum drying that temperature is 100 DEG C~103 DEG C
In case it is dry for 24 hours, the phenolic resin charcoal powder that obtains that treated.Other steps are identical as specific embodiment one to five.
Specific embodiment 7: one of present embodiment and specific embodiment one to six difference are: institute in step 4
The volume ratio for the methanol solution that the quality of the phenolic resin charcoal powder for the drying stated and mass fraction are 37% be (10g~
13g):100mL.Other steps are identical as specific embodiment one to six.
Specific embodiment 8: one of present embodiment and specific embodiment one to seven difference are: institute in step 4
The volume ratio for the sodium hydroxide solution that the quality of the phenolic resin charcoal powder for the drying stated is 20% with mass fraction is
(10g~13g): 10mL.Other steps are identical as specific embodiment one to seven.
Specific embodiment 9: one of present embodiment and specific embodiment one to eight difference are: institute in step 5
The quality of phenolic resin charcoal powder of stating that treated and the volume ratio of n-hexane are (0.01g~0.03g): 70mL.Its
His step is identical as specific embodiment one to eight.
Specific embodiment 10: one of present embodiment and specific embodiment one to nine difference are: institute in step 6
The quality for the dimethyl silicone polymer stated and the volume ratio of n-hexane are (0.8g~0.9g): 70mL.Other steps and specific reality
It is identical to apply mode one to nine.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one: a kind of preparation method of phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane, tool
Body is completed by the following steps:
One, it prepares phenolic resin charcoal: bark is clayed into power, then dried for 24 hours at being 105 DEG C in temperature, done
Dry bark fines；Dry bark fines are mixed with phenolic resin again, then low whipping speed is that magnetic force stirs under 180r/min
4h is mixed, the mixture of dry bark fines and phenolic resin is obtained；By the mixture of dry bark fines and phenolic resin
Solidify 2h in the case where pressure is 10MPa and temperature is 180 DEG C, then high-temperature process 1h at being 300 DEG C in nitrogen atmosphere and temperature, obtains
Phenolic resin charcoal；
Bark described in step 1 is shore pipe bark；
The bark fines of drying described in step 1 and the mass ratio of phenolic resin are 1:1；
Two, phenolic resin charcoal is ground, then at being 120 DEG C in temperature it is dry for 24 hours, obtain partial size be 50nm~
The phenolic resin charcoal powder of 60nm；
Three, the phenolic resin charcoal powder that partial size is 50nm~60nm is wrapped up using filter paper, then is placed in rope
It in family name's extractor, then uses toluene for solvent, extracts under nitrogen protection for 24 hours, the biological powdered carbon after being extracted；After extracting
Biological powdered carbon be dried at normal temperature, obtain dry phenolic resin charcoal powder；
Four, by dry phenolic resin charcoal powder, mass fraction be 37% methanol solution and mass fraction be
20% sodium hydroxide solution mixing, then the magnetic agitation 5h in the case where temperature is 50 DEG C and mixing speed is 180r/min, then it is natural
It is cooled to room temperature, reuses distilled water and clean 4 times, be finally putting into drying in the vacuum oven that temperature is 103 DEG C and for 24 hours, obtain
Phenolic resin charcoal powder that treated；
The quality of the phenolic resin charcoal powder of drying described in step 4 and the methanol that mass fraction is 37% are molten
The volume ratio of liquid is 10g:100mL；
The hydroxide that the quality and mass fraction of the phenolic resin charcoal powder of drying described in step 4 are 20%
The volume ratio of sodium solution is 10g:10mL；
Five, by treated, phenolic resin charcoal powder, vinyltriethoxysilane and n-hexane are mixed, and are mixed
Liquid I is closed, ultrasonic oscillation device is reused and 30min is handled to I ultrasonic vibration of mixed liquor, then low whipping speed is magnetic under 180r/min
Power stirs 60min, obtains uniform mixed liquor I；
The mass ratio of vinyltriethoxysilane described in step 5 and treated phenolic resin charcoal powder
For 1:1；
The quality of phenolic resin charcoal powder that treated described in step 5 and the volume ratio of n-hexane are
(0.015g~0.045g): 70mL；
Six, dimethyl silicone polymer and n-hexane are mixed, then low whipping speed is magnetic agitation 1h under 180r/min, is obtained
To mixed liquor II；
The quality of dimethyl silicone polymer described in step 6 and the volume ratio of n-hexane are 1g:70mL；
Seven, uniform mixed liquor I and mixed liquor II are mixed, then low whipping speed is magnetic agitation under 180r/min
60min adds ethyl orthosilicate, then low whipping speed is magnetic agitation 60min under 180r/min, adds dilaurate two
Butyl tin, then low whipping speed are magnetic agitation 10min under 180r/min, obtain mixed solution III；
The volume ratio of ethyl orthosilicate described in step 7 and mixed liquor II is 1:1200；
Dibutyl tin dilaurate described in step 7 and the volume ratio of mixed liquor II are 1:8000；
Eight, cellulose acetate microfiltration membranes are impregnated into 2h in deionized water, cellulose acetate microfiltration membranes is wiped out after taking-up
The deionized water on surface, then mixed solution III is cast in into removal surface under conditions of temperature is 25 DEG C and humidity is 55%
In the cellulose acetate microfiltration membranes of ionized water, knifing is carried out in cellulose acetate microfiltration membranes using knifing machine in casting process,
Then the cellulose acetate microfiltration membranes for being cast with mixed solution III are placed into 20h~28h again at room temperature, then in temperature are 80 DEG C
Baking oven in dry 8h, obtain phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane；
The mass ratio of mixed solution III described in step 8 and cellulose acetate micro-nano filter membrane is 100:10.
Treated described in step 5 in embodiment one quality of phenolic resin charcoal powder and the body of n-hexane
The infrared song of treated the phenolic resin biology powdered carbon obtained in step 4 of embodiment one is measured when product is than for 0.03g:70mL
The infrared curve of line and treated the phenolic resin biology powdered carbon obtained in step 4 of embodiment one, as shown in Figure 1；
Fig. 1 is infrared spectrogram, and 1 is treated the phenolic resin charcoal obtained in step 4 of embodiment one in Fig. 1
The infrared curve of powder, 2 be the infrared of the powder that obtains after I solvent flashing of uniform mixed liquor obtained in one step 5 of embodiment
Curve；
From fig. 1, it can be seen that the modified biological powdered carbon of vinyltriethoxysilane and unmodified treated phenolic resin
There is apparent change in the infrared spectroscopy comparison of biological powdered carbon.Unmodified treated the phenolic resin charcoal from Fig. 1
Pink external curve, which can be seen that, there is a small amount of CH2Stretching vibration peak (2800-3000cm-1), mainly vinyl triethoxyl
The vinyl characteristic peak of silane.In addition, the curve for the biological powdered carbon that vinyltriethoxysilane is modified can be in 1031cm-1It sees
An apparent Si-O characteristic peak is observed, both the characteristic absorption peak of vinyltriethoxysilane.According to infrared spectroscopy
Analysis, it can be deduced that the group of silane coupling agent is successfully grafted to that treated phenolic resin biology powdered carbon surface.Determine biology
The hydroxyl on powdered carbon surface is chemically reacted with three second methoxy silane of vinyl, the ethylene on the biological powdered carbon surface grafting
The functional group of ethyl triethoxy silicane alkane.
Embodiment two: the present embodiment and the difference of embodiment one are: one, preparing phenolic resin charcoal: bark is ground
At powder, then is dried at being 105 DEG C in temperature and obtain dry bark fines for 24 hours；Again by dry bark fines and phenolic aldehyde tree
Rouge mixing, then low whipping speed is magnetic agitation 4h under 180r/min, obtains the mixing of dry bark fines and phenolic resin
Object；The mixture of dry bark fines and phenolic resin is solidified into 2h in the case where pressure is 10MPa and temperature is 180 DEG C, then
Nitrogen atmosphere and temperature are high-temperature process 1h at 600 DEG C, obtain phenolic resin charcoal.Other are the same as example 1.
Embodiment three: the present embodiment and the difference of embodiment one are: one, preparing phenolic resin charcoal: bark is ground
At powder, then is dried at being 105 DEG C in temperature and obtain dry bark fines for 24 hours；Again by dry bark fines and phenolic aldehyde tree
Rouge mixing, then low whipping speed is magnetic agitation 4h under 180r/min, obtains the mixing of dry bark fines and phenolic resin
Object；The mixture of dry bark fines and phenolic resin is solidified into 2h in the case where pressure is 10MPa and temperature is 180 DEG C, then
Nitrogen atmosphere and temperature are high-temperature process 1h at 900 DEG C, obtain phenolic resin charcoal.Other are identical as embodiment two.
Fig. 2 is that the additive amount of treated phenolic resin biology powdered carbon enhances ethyl alcohol selection to phenol-formaldehyde resin modified charcoal
Property infiltrating and vaporizing membrane surface and water contact angle influence diagram, 1 is raw for the phenol-formaldehyde resin modified for preparing in embodiment one in Fig. 2
Object charcoal enhances the surface of ethanol selectivity infiltrating and vaporizing membrane and the contact angle curve of water, the 2 modification phenol to prepare in embodiment two
Urea formaldehyde charcoal enhances the surface of ethanol selectivity infiltrating and vaporizing membrane and the contact angle curve of water, and 3 be to prepare in embodiment three
Phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane surface and water contact angle curve；
Figure it is seen that preparing phenol-formaldehyde resin modified biology using the phenolic resin charcoal prepared under different temperatures
The contact angle of charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane and water is far longer than the selectivity infiltration for being not added with phenolic resin charcoal
Vaporization film thoroughly；With phenolic resin charcoal additive amount in phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane
Gradually increase, phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane and the contact angle of water are also gradually increased.
This illustrates that the hydrophobicity of phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane significantly improves.By phenolic resin
The modification of charcoal, phenolic resin biology carbon surface contain hydrophobic grouping, increase the phenol-formaldehyde resin modified charcoal of preparation
The surface hydrophobic of strong ethanol selectivity infiltrating and vaporizing membrane is effectively improved.
Fig. 3 is that the additive amount of treated phenolic resin biology powdered carbon enhances ethyl alcohol selection to phenol-formaldehyde resin modified charcoal
Property infiltrating and vaporizing membrane surface and dehydrated alcohol contact angle influence diagram, 1 modified phenolic to be prepared in embodiment one in Fig. 3
Resin charcoal enhances the surface of ethanol selectivity infiltrating and vaporizing membrane and the contact angle curve of dehydrated alcohol, and 2 is in embodiments two
The surface of the phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane of preparation and the contact angle curve of dehydrated alcohol,
3 be surface and the dehydrated alcohol that the phenol-formaldehyde resin modified charcoal prepared in embodiment three enhances ethanol selectivity infiltrating and vaporizing membrane
Contact angle curve；
From figure 3, it can be seen that preparing phenol-formaldehyde resin modified biology using the phenolic resin charcoal prepared under different temperatures
The contact angle of charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane and dehydrated alcohol is seeped with the selectivity for being not added with phenolic resin charcoal
Vaporization film is compared thoroughly, the phenol-formaldehyde resin modified charcoal that is prepared at a temperature of three kinds enhancing ethanol selectivity infiltrating and vaporizing membrane with it is anhydrous
All there is apparent reduction in the contact angle of ethyl alcohol.This illustrates that phenol-formaldehyde resin modified charcoal enhances ethanol selectivity infiltration evaporation
The compatibility of film and ethyl alcohol greatly improves, and difference prepares the temperature (300 DEG C, 600 DEG C and 900 DEG C) of phenolic resin to modified phenolic
Resin charcoal enhance ethanol selectivity infiltrating and vaporizing membrane in ethyl alcohol contact angle almost without difference.
Embodiment five: claying into power bark in step 1, then dries at being 105 DEG C in temperature and obtain dry tree for 24 hours
Skin powder；Dry bark fines are mixed with phenolic resin again, then low whipping speed is magnetic agitation 4h under 180r/min, is obtained
To the mixture of dry bark fines and phenolic resin；Mixture by dry bark fines and phenolic resin is in pressure
10MPa and temperature are to solidify 2h at 180 DEG C, then high-temperature process 1h at being 600 DEG C in nitrogen atmosphere and temperature obtains phenolic resin
Charcoal；The quality for phenolic resin charcoal powder that treated described in step 5 and the volume ratio of n-hexane are 0.03g:
70mL；The mass ratio of vinyltriethoxysilane described in step 5 and treated phenolic resin charcoal powder is
0.5:1.Other are the same as example 1.
Embodiment six: claying into power bark in step 1, then dries at being 105 DEG C in temperature and obtain dry tree for 24 hours
Skin powder；Dry bark fines are mixed with phenolic resin again, then low whipping speed is magnetic agitation 4h under 180r/min, is obtained
To the mixture of dry bark fines and phenolic resin；Mixture by dry bark fines and phenolic resin is in pressure
10MPa and temperature are to solidify 2h at 180 DEG C, then high-temperature process 1h at being 600 DEG C in nitrogen atmosphere and temperature obtains phenolic resin
Charcoal；The quality for phenolic resin charcoal powder that treated described in step 5 and the volume ratio of n-hexane are 0.03g:
70mL.Other are the same as example 1.
Embodiment seven: claying into power bark in step 1, then dries at being 105 DEG C in temperature and obtain dry tree for 24 hours
Skin powder；Dry bark fines are mixed with phenolic resin again, then low whipping speed is magnetic agitation 4h under 180r/min, is obtained
To the mixture of dry bark fines and phenolic resin；Mixture by dry bark fines and phenolic resin is in pressure
10MPa and temperature are to solidify 2h at 180 DEG C, then high-temperature process 1h at being 600 DEG C in nitrogen atmosphere and temperature obtains phenolic resin
Charcoal；The quality for phenolic resin charcoal powder that treated described in step 5 and the volume ratio of n-hexane are 0.03g:
70mL；The mass ratio of vinyltriethoxysilane described in step 5 and treated phenolic resin charcoal powder is 2:
1.Other are the same as example 1.
Fig. 4 is vinyltriethoxysilane with the ratio of treated phenolic resin biology powdered carbon to composite membrane separation property
Can influence, A is that phenol-formaldehyde resin modified charcoal obtained in embodiment five enhances ethanol selectivity infiltrating and vaporizing membrane in Fig. 4
The histogram of total permeation flux, B are that phenol-formaldehyde resin modified charcoal obtained in embodiment five enhances ethanol selectivity infiltration vapour
Change the histogram of the ethanol infiltration flux of film, C is that phenol-formaldehyde resin modified charcoal obtained in embodiment five enhances ethyl alcohol selection
Property infiltrating and vaporizing membrane water penetration flux histogram, D be embodiment six obtained in phenol-formaldehyde resin modified charcoal enhance second
Alcohol selectively penetrating vaporizes the histogram of total permeation flux of film, and E is phenol-formaldehyde resin modified charcoal obtained in embodiment six
Enhance the histogram of the ethanol infiltration flux of ethanol selectivity infiltrating and vaporizing membrane, F is modified phenolic resin obtained in embodiment six
Rouge charcoal enhances the histogram of the water penetration flux of ethanol selectivity infiltrating and vaporizing membrane, and G is the modification phenol that embodiment seven obtains
Urea formaldehyde charcoal enhances total permeation flux histogram of ethanol selectivity infiltrating and vaporizing membrane, and H is to change obtained in embodiment seven
Property phenolic resin charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane ethanol infiltration flux histogram, I be embodiment seven in
The histogram of the water penetration flux of obtained phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane；
Separation temperature in Fig. 4 is 40 DEG C, as can be seen from Figure 4, vinyltriethoxysilane/and treated, and phenolic resin is raw
The ratio of object powdered carbon increases, and the permeation flux of phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane can gradually drop
It is low.When the ratio of vinyltriethoxysilane/treated phenolic resin biology powdered carbon is 1:1, phenol-formaldehyde resin modified biology
Charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane reaches maximum value to the ethanol infiltration flux ratio of ethanol water, while to water
It is then minimum.
Fig. 5 is vinyltriethoxysilane with the ratio of treated phenolic resin biology powdered carbon to phenol-formaldehyde resin modified
Charcoal enhances the influence diagram of ethanol selectivity infiltrating and vaporizing membrane separation, 1 modified phenolic prepared for embodiment five in Fig. 5
Resin charcoal enhances the separation factor histogram of ethanol selectivity infiltrating and vaporizing membrane, 2 modified phenolics prepared for embodiment six
Resin charcoal enhances the separation factor histogram of ethanol selectivity infiltrating and vaporizing membrane, 3 modified phenolics prepared for embodiment seven
The separation factor histogram of resin charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane；
Separation temperature in Fig. 5 is 40 DEG C, as can be seen from Figure 5, vinyltriethoxysilane/and treated, and phenolic resin is raw
The ratio of object powdered carbon increases, and the permeation flux of phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane can gradually drop
It is low.When the ratio of vinyltriethoxysilane/treated phenolic resin biology powdered carbon is 1:1, phenol-formaldehyde resin modified biology
Charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane reaches maximum value to the ethanol infiltration flux ratio in ethanol water, while to water
It is then minimum value.When the ratio of alkenyl triethoxysilane/treated phenolic resin biology powdered carbon is 1:1, modified phenolic resin
The separation that rouge charcoal enhances ethanol selectivity infiltrating and vaporizing membrane is best, can achieve 11.4, is primarily due to silicon
The coupling agent modified biological carbon surface of alkane becomes hydrophobic, will continue to that chemistry occurs with the hydroxyl of dimethyl silicone polymer end instead
It answers, makes being cross-linked with each other for polymeric.After polymeric is cross-linked with each other, free volume is obtained in separation one polymer
It tails off, the ethanol molecule and hydrone number that will lead to permeation composite membrane tail off.
The ratio of vinyltriethoxysilane/treated phenolic resin biology powdered carbon, which increases, to be increased, and can make to handle
The hydrophobicity of phenolic resin biology powdered carbon afterwards enhances, and mixes with dimethyl silicone polymer matrix more uniform, therefore, works as second
For alcohol molecule in separating layer when diffusion, phenol-formaldehyde resin modified charcoal enhances the segregative line of ethanol selectivity infiltrating and vaporizing membrane
Number, which will appear, to be significantly improved.The ratio of vinyltriethoxysilane/treated phenolic resin biology powdered carbon is excessive, is greater than 2:
When 1, extra silane coupling agent will lead to the segment arrangement for destroying polymeric matrix, and phenol-formaldehyde resin modified charcoal enhances ethyl alcohol
There is defect in selectively penetrating vaporization film, and the separating property for being eventually exhibited as composite membrane reduces.
Separation temperature in Fig. 6 is 40 DEG C, and the additive amount of Fig. 6 is that treated phenolic resin biology powdered carbon is to modified phenolic
Resin charcoal enhances the influence diagram of the permeation flux of ethanol selectivity infiltrating and vaporizing membrane；1 is to prepare in embodiment one in Fig. 6
Phenol-formaldehyde resin modified charcoal enhances the curve of the permeation flux of ethanol selectivity infiltrating and vaporizing membrane, and 2 be to prepare in embodiment two
Phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane permeation flux curve, 3 is make in embodiment three
The curve of the permeation flux of standby phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane；
As can be seen from Figure 6,3% or more, permeation flux is no longer obviously improved the additive amount of phenolic resin charcoal, is protected
It holds in more stable state.
Separation temperature in Fig. 7 is 40 DEG C, and the additive amount of Fig. 7 is that treated phenolic resin biology powdered carbon is to modified phenolic
Resin charcoal enhances the influence diagram of the separation factor of ethanol selectivity infiltrating and vaporizing membrane；1 is to prepare in embodiment one in Fig. 7
Phenol-formaldehyde resin modified charcoal enhances the separation factor curve of ethanol selectivity infiltrating and vaporizing membrane, and 2 be to prepare in embodiment two
Phenol-formaldehyde resin modified charcoal enhances the separation factor curve of ethanol selectivity infiltrating and vaporizing membrane, and 3 be to prepare in embodiment three
The separation factor curve of phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane；
As can be seen from Figure 7, after the addition of phenolic resin biology powdered carbon, phenol-formaldehyde resin modified charcoal enhances ethanol selectivity
The separation of infiltrating and vaporizing membrane significantly increases, and separation is gradually increased with phenolic resin charcoal additive amount, first
It increases rapidly, when the additive amount of phenolic resin charcoal is 3%, separation is best, rear to gradually decrease again.
Phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane prepared by embodiment six is placed in film test
In device, unlocking testing device, runs one hour, tests the infiltration evaporation performance of composite membrane every twenty-four hours.Such as Fig. 8 institute
Show；Abscissa in Fig. 8 is that phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane prepared by embodiment six is set
Time in film test device；
Fig. 8 is the operating time to enhance ethanol selectivity infiltration evaporation to phenol-formaldehyde resin modified charcoal prepared by embodiment six
The curve that film infiltration evaporation performance influences, 1 phenol-formaldehyde resin modified charcoal increasing prepare by embodiment six for the operating time in Fig. 8
The curve that strong ethanol selectivity infiltrating and vaporizing membrane permeation flux influences, 2 modification prepared by embodiment six for the operating time in Fig. 8
Phenolic resin charcoal enhances the curve that ethanol selectivity infiltrating and vaporizing membrane separation factor influences.
Separation temperature in Fig. 8 is 40 DEG C, from figure 8, it is seen that the continuous experiment composite membrane by 168 hours does not go out
The phenomenon that incumbent absciss layer is removed, it can be verified that separating layer and the bond strength of supporting layer are very high.Show prepared by embodiment six simultaneously
Phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane the Long Term Contact with transparent liquid for seep, separating layer do not have
Appearance swellbility is excessive, illustrates phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane tool prepared by embodiment six
There is extraordinary swelling resistivity.
Claims (1)
1. a kind of preparation method of phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane, it is characterised in that the party
What method was specifically realized by the following steps:
One, it prepares phenolic resin charcoal: bark is clayed into power, then dried for 24 hours at being 105 DEG C in temperature, obtain drying
Bark fines；Dry bark fines are mixed with phenolic resin again, then low whipping speed is magnetic agitation 4h under 180r/min,
Obtain the mixture of dry bark fines and phenolic resin；By the mixture of dry bark fines and phenolic resin in pressure
It is to solidify 2h at 180 DEG C for 10MPa and temperature, then high-temperature process 1h at being 600 DEG C in nitrogen atmosphere and temperature obtains phenolic aldehyde tree
Rouge charcoal；
Bark described in step 1 is shore pipe bark；
The bark fines of drying described in step 1 and the mass ratio of phenolic resin are 1:1；
Two, phenolic resin charcoal is ground, then is dried for 24 hours at being 120 DEG C in temperature, obtaining partial size is 50nm~60nm
Phenolic resin charcoal powder；
Three, the phenolic resin charcoal powder that partial size is 50nm~60nm is wrapped up using filter paper, then is placed in Soxhlet pumping
It mentions in device, then uses toluene for solvent, extract under nitrogen protection for 24 hours, the biological powdered carbon after being extracted；By the life after extracting
Object powdered carbon is dried at normal temperature, obtains dry phenolic resin charcoal powder；
Four, by dry phenolic resin charcoal powder, mass fraction be 37% methanol solution and mass fraction be 20%
Sodium hydroxide solution mixing, then the magnetic agitation 5h in the case where temperature is 50 DEG C and mixing speed is 180r/min, then naturally cool to
Room temperature reuses distilled water and cleans 4 times, is finally putting into the vacuum oven that temperature is 103 DEG C and dries for 24 hours, after obtaining processing
Phenolic resin charcoal powder；
The methanol solution that the quality and mass fraction of the phenolic resin charcoal powder of drying described in step 4 are 37%
Volume ratio is 10g:100mL；
The quality of the phenolic resin charcoal powder of drying described in step 4 and the sodium hydroxide that mass fraction is 20% are molten
The volume ratio of liquid is 10g:10mL；
Five, by treated, phenolic resin charcoal powder, vinyltriethoxysilane and n-hexane are mixed, and obtain mixed liquor
I, it reuses ultrasonic oscillation device and 30min is handled to I ultrasonic vibration of mixed liquor, then low whipping speed is that magnetic force stirs under 180r/min
60min is mixed, uniform mixed liquor I is obtained；
The mass ratio of vinyltriethoxysilane described in step 5 and treated phenolic resin charcoal powder is 1:
1；
The quality for phenolic resin charcoal powder that treated described in step 5 and the volume ratio of n-hexane are 0.03g:
70mL；
Six, dimethyl silicone polymer and n-hexane are mixed, then low whipping speed is magnetic agitation 1h under 180r/min, is mixed
Close liquid II；
The quality of dimethyl silicone polymer described in step 6 and the volume ratio of n-hexane are 1g:70mL；
Seven, uniform mixed liquor I and mixed liquor II are mixed, then low whipping speed is magnetic agitation 60min under 180r/min, then
Ethyl orthosilicate is added, then low whipping speed is magnetic agitation 60min under 180r/min, adds dibutyl tin dilaurate,
Low whipping speed is magnetic agitation 10min under 180r/min again, obtains mixed solution III；
The volume ratio of ethyl orthosilicate described in step 7 and mixed liquor II is 1:1200；
Dibutyl tin dilaurate described in step 7 and the volume ratio of mixed liquor II are 1:8000；
Eight, cellulose acetate microfiltration membranes are impregnated into 2h in deionized water, cellulose acetate micro-filtration film surface is wiped out after taking-up
Deionized water, then mixed solution III is cast in into removal surface deionization under conditions of temperature is 25 DEG C and humidity is 55%
In the cellulose acetate microfiltration membranes of water, knifing is carried out in cellulose acetate microfiltration membranes using knifing machine in casting process, then
The cellulose acetate microfiltration membranes for being cast with mixed solution III are placed into 20h~28h, then the baking for being 80 DEG C in temperature at room temperature again
Dry 8h in case obtains phenol-formaldehyde resin modified charcoal enhancing ethanol selectivity infiltrating and vaporizing membrane；
The mass ratio of mixed solution III described in step 8 and cellulose acetate micro-nano filter membrane is 100:10.
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| Application of PDMS pervaporation membranes filled with tree bark biochar for ethanol/water separation;Yongqiang Lan, et al.,;《RSC Advances》;20160506;第6卷;第47637-47645页 |
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